CN106995668A - Assign resin, contact adhesive/adhesive, the hot melt adhesive of adherence - Google Patents
Assign resin, contact adhesive/adhesive, the hot melt adhesive of adherence Download PDFInfo
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- CN106995668A CN106995668A CN201611160305.4A CN201611160305A CN106995668A CN 106995668 A CN106995668 A CN 106995668A CN 201611160305 A CN201611160305 A CN 201611160305A CN 106995668 A CN106995668 A CN 106995668A
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- Prior art keywords
- resin
- rosin
- adhesive
- acid
- adherence
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
- C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
- C09J123/04—Homopolymers or copolymers of ethene
- C09J123/08—Copolymers of ethene
- C09J123/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
- C09J123/0853—Vinylacetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The present invention provides a kind of resin for assigning adherence, its impartings adherence as hot melt adhesive resin and in use, with the intermiscibility of matrix resin well, and the thermal-stable of the hot melt adhesive can be improved and its melt viscosity can be reduced.The present invention is the resin of the imparting adherence containing rosin ester (A), wherein, rosin ester (A) be with rosin (a1) and polyalcohol (a2) containing binary diterpene carboxylic acid be reacted constituent obtained from.
Description
Technical field
The present invention relates to the resin of imparting adherence, contact adhesive/adhesive of the resin containing the imparting adherence
And the hot melt adhesive of the resin containing the imparting adherence.
In this manual, " contact adhesive/adhesive (being bonded drug) " refers to contact adhesive and/or gluing
Agent；" hot melt adhesive " is referred to be applied with molten condition on supporting mass, forms the gluing of bonding layer to cool and solidify state
Agent (more than, referring to JIS K 6800)
Background technology
The reaction product rosin ester of rosin and polyalcohol is as the resin for assigning adherence, in hot melt adhesive, solvent-borne type
Received an acclaim in contact adhesive/adhesive and emulsion-type pressure sensitive adhesive/adhesive etc. (referring to patent document 1-3).
Use above-mentioned contact adhesive/adhesive under the high temperature conditions sometimes, in this case, as rosin ester, make
With the rosin ester of high softening-point.It is known to have for example, make the α such as fumaric acid as the rosin ester of the high softening-point so used, β-
The so-called fortified rosin and the reaction product (fortified rosin ester) of polyalcohol that unsaturated carboxylic acid and rosin react and generated are (referring to special
Sharp document 4 and 5).
On the other hand, conventional fortified rosin ester the imparting adherence as hot melt adhesive resin and in use,
There is a situation where with matrix resin, particularly ethylene-vinyl acetate copolymer intermiscibility it is insufficient.Moreover, containing the rosin
The hot melt adhesive of ester appears in the insufficient situations of thermal-stable such as muddy during heating and generation peeling and because of melting
The situation that viscosity is high, coating workability is insufficient.
Prior art literature
Patent document
[patent document 1] Japanese Kohyo 6-501515 publications
[patent document 2] Japanese Unexamined Patent Publication 9-25371 publications
[patent document 3] Japanese Unexamined Patent Publication 2010-77429 publications
[patent document 4] Japanese Unexamined Patent Application 60-28476 publications
[patent document 5] Japanese Unexamined Patent Application 63-275685 publications
The content of the invention
The invention technical problem to be solved
The problem of the present invention is to provide a kind of resin of the imparting adherence of new rosin ester type, and it is being used as melt viscosity
The resin of the imparting adherence of agent can reduce the hot melt adhesive in use, good with the intermiscibility of matrix resin
Melt viscosity and its thermal-stable can be improved.
Solve the technological means of technical problem
Inventors believe that, conventional fortified rosin ester contains much such as with the polynary resin acid of following representations,
Because polynary resin acid as branch point allows to carry out abnormal molecular weight, so difficult with the matrix resin of hot melt adhesive
In mixing.
[changing 2]
In order to reduce the molecular weight of fortified rosin ester, as long as reducing α, usage amount, the reduction reinforcing journey of beta-unsaturated carboxylic acid
Degree, however, the fortified rosin ester of such low molecule amount causes the melt viscosity of hot melt adhesive to significantly reduce, also makes to add
Heat endurance is deteriorated.
Here, the present inventor is to without using α, beta-unsaturated carboxylic acid can also realize that the raw material rosin of molecular weight is dived
The result of heart research is found, by using the rosin containing the binary resin acid for being imbued with reactivity, can must reach expected effect
The resin of the imparting adherence of fruit.
That is, the present invention relates to：The resin of imparting adherence containing rosin ester (A) and the tree containing the imparting adherence
Contact adhesive/the adhesive and hot melt adhesive of fat and matrix resin, wherein, rosin ester (A) is with containing binary diterpene
The rosin (a1) and polyalcohol (a2) of carboxylic acid are as obtained from reacted constituent.
Invention effect
The rosin ester of the resin of the imparting adherence of the present invention, because containing binary diterpene carboxylic acid, even without α, β-
It is unsaturated carboxylic acid-modified, it can also realize and the equal performance above of conventional fortified rosin ester.
Specifically, the resin of imparting adherence of the invention can provide matrix resin with hot melt adhesive, spy
Be not ethylene-vinyl acetate copolymer intermiscibility is good, homogeneous clear hot melt adhesive.Moreover, involved in the present invention
Hot melt adhesive because melt viscosity is relatively small, coating workability is good, and then thermal-stable is also good, therefore,
The problem of also being difficult to produce muddy and peeling even if long-time heating.Moreover, the hot melt adhesive is in terms of heat-resisting confining force
It is excellent.
The resin of the imparting adherence of the present invention is applied to the purposes of hot melt adhesive, is also applied for solvent-borne type pressure-sensitive adhesion
Agent/adhesive and emulsion-type pressure sensitive adhesive/adhesive etc..
Embodiment
The present invention imparting adherence resin (hereinafter referred to as composition) be containing rosin ester (A) (hereinafter referred to as (A) into
Point) composition, wherein, rosin ester (A) be containing the binary diterpene carboxylic acid represented with following structural formula rosin (a1) (with
Lower abbreviation (a1) composition) and polyalcohol (a2) be reacted constituent obtained from.
[changing 3]
Binary diterpene carboxylic acid according to its alloisomerism construction can be categorized as dihydro agathic acid (ジ ヒ De ロ ア ガ ト acid),
オ リ ベ リ acid, エ ペ Le エ Application ジ カ Le ボ Application acid and ピ ニ Off ォ リ Application acid.Following presentation dihydro agathic acid (Formulas I), オ リ ベ リ
The construction of sour (Formula II), エ ペ Le エ Application ジ カ Le ボ Application sour (formula III) and ピ ニ Off ォ リ Application sour (formula IV).
[changing 4]
The binary diterpene carboxylic acid is incorporated into the special tectonic of alicyclic ring skeleton with primary carboxyl by soft alkyl chain.And
And, the primary carboxyl-reactive is high, is easily reacted with (a2) described later, easily forms high molecular weight polyesters.Following presentation should
The non-limiting structure of polyester.
[changing 5]
It may be speculated that (A) composition is because containing the polyester with the as above molecular skeleton of feature, even if not being reinforced
It is modified, it may have with the equal action effect above of conventional fortified rosin ester.
(a1) content of the foregoing binary diterpene carboxylic acid in composition is not particularly restricted, however, the content of the carboxylic acid is too
If few, there is the tendency of reduction in the softening point step-down of (A) composition, foregoing heat-resisting confining force.Moreover, the content of the carboxylic acid is too many
If, the molecular weight of (A) composition is uprised, and foregoing intermiscibility and thermal-stable are deteriorated, and aforementioned melt viscosity is also relative to be uprised, and is deposited
The tendency being deteriorated in coating workability.Come from the viewpoint of the balance of heat-resisting confining force, intermiscibility, thermal-stable and melt viscosity
See, the content of binary diterpene carboxylic acid is typically less than 20 weight %, preferably 1-15 weight % or so, be more preferably 3-13 weights
Measure % or so.
As (a1) composition, such as following scheme can be enumerated：
(I)：The original rosin containing binary diterpene carboxylic acid；
(II)：(I) composition combines the rosin to be formed with the rosin without binary diterpene carboxylic acid；
(III)：The rosin that dihydro agathic acid is formed with rosin and/or (I) without binary diterpene carboxylic acid into subassembly.
As (I) composition, as long as the rosin containing binary diterpene carboxylic acid, no matter the then place of production and pine tree kind.For example,
In the rosin of Indonesia's production and the rosin of Vietnam's production, contain more binary diterpene carboxylic acid.Especially in Indonesia's production
In the rosin (gum rosin, Starex, wood rosin etc.) for coming from Nan Yang loose (Pinus merkusii) produced with Vietnam, contain
Special dihydro agathic acid.Furthermore, it is also possible to use the hydride and disproportionation thing of the rosin.
(I) composition can also use various known methods to be refined.Specifically, for example, distillation, again can be enumerated
The operation such as crystallization and extraction.The condition of distillation is not particularly restricted, and typical temperature is 200-300 DEG C or so and pressure is
130-1300Pa or so.Recrystallization is as follows：(I) composition is dissolved in benzene,toluene,xylene, chloroform, lower alcohol, acetone, acetic acid
After the good solvents such as ethyl ester, the good solvent is distilled off, as concentrated solution, n-hexane, normal heptane, hexamethylene are added to the solution
The lean solvents such as alkane, isooctane.Extract as follows：Aqueous alkali is made in (I) composition, insoluble unsaponifiable matter is used into conjunction
After suitable solution is extracted, water layer is neutralized.
As the rosin without binary diterpene carboxylic acid for constituting (II) composition, it can use various known without binary two
The rosin of terpene carboxylic acid, it is not particularly restricted.Specifically, it can enumerate for example：The days such as gum rosin, Starex, wood rosin
Right rosin；The resin that natural rosin is refining to obtain；Natural rosin is subjected to the hydrogenated rosin that hydrogenation is obtained；By day
Right rosin carries out disproportionated rosin that disproportionated reaction is obtained etc..
As the binary diterpene carboxylic acid for constituting (III) composition, it is, for example, possible to use Japanese Unexamined Patent Application 51-131899 public affairs
The method that report is recorded is prepared.
In (a1) composition, as the resin acid beyond binary diterpene carboxylic acid, it can contain for example, rosin acid and dehydrogenation pine
Fragrant acid.Their content is not particularly restricted, typically respectively less than 60 weight % and less than 30 weight %, is preferably respectively
20-50 weight % or so and 5 weight % or so.
(a1) content of the resin acid in composition can use various known methods to quantify.For example, using gas-chromatography
(GC), tried to achieve by the peak area of the resin acid by quantitative objective is come from divided by the peak area of total resin acid.
(a1) physical characteristic of composition is not particularly restricted, it is however generally that, softening point is usually a 70-90 DEG C of left side
The right side, moreover, acid number is usually 130-200mgKOH/g or so.
As (a2) composition, various known polyalcohols can be used.Specifically, it can enumerate for example：Ethylene glycol, two
The dihydric alcohols such as ethylene glycol, triethylene glycol, propane diols, neopentyl glycol, dimer diol and 1,6-HD；Glycerine, trihydroxy methyl second
The trihydroxylic alcohols such as alkane, trimethylolpropane；The tetrahydroxylic alcohols such as pentaerythrite；Polyalcohol that more than 5 yuan of dipentaerythritol etc. etc., can also
It is two or more to be used together.Wherein, it is considered to the intermiscibility and pressure-sensitive adhesion involved in the present invention of (A) composition and matrix resin
If the performance of agent/adhesive, what is selected in the group preferably constituted from dihydric alcohol, trihydroxylic alcohol and tetrahydroxylic alcohol is at least one polynary
Alcohol.
(a2) usage amount of composition is not particularly restricted, however, especially considering the adhesion such as heat-resisting confining force/glueability
If, acid number (the JIS K 0070 of (a1) composition；Hereinafter, it is same when referring to acid number) and (a2) composition in hydroxyl value
(JIS K 0070；Hereinafter, it is same when referring to hydroxyl value) ratio (OH/COOH) generally in the range of 0.5-4 or so
Preferably.
As needed, various known α, beta-unsaturated carboxylic acid class (a3) can be contained in the reacted constituent of (A) composition
(hereinafter referred to as (a3) composition).Specifically, it can enumerate for example：The α, β such as acrylic acid and methacrylic acid-unsaturation unitary carboxylic
Acid etc.；And the α such as fumaric acid and maleic acid (acid anhydride), β-unsaturated dicarboxylic acid etc., two or more it can also be used together.
(a3) usage amount of composition is not particularly restricted, however, it is contemplated that the resin and base of the imparting adherence of the present invention
If intermiscibility of body polymer etc., it is however generally that, relative to 1 mole of rosin acid in (a1) composition, the use of (a3) composition
Amount is usually 0.005-3 moles or so, more preferably in the range of 0.005-0.3 moles or so.
As (A) composition, such as following scheme can be enumerated：
(A1)：(a1) carboxylate (rosin ester) of composition and (a2) composition；
(A2)：(A1) the Diels-Alder reaction product (fortified rosin ester) of composition and (a3) composition；
(A3)：(a1) carboxylate (the reinforcing pine of the Diels-Alder reaction thing of composition and (a3) composition and (a2) composition
Fragrant ester)；
(A4)：(a1) reaction product (fortified rosin ester) while composition, (a2) composition and (a3) composition.
The condition of esterification is not particularly restricted, for example, previous reaction composition in the presence of solvent or is not present
Under, and in the presence of esterification catalyst or in the absence of, enter under conditions of 250-280 DEG C or so and 1-8 hours or so
Row reaction.As the esterification catalyst, it can enumerate for example：The acid catalysts such as p-methyl benzenesulfonic acid；The alkaline earths such as calcium hydroxide
The hydroxide of metal；Metal oxides such as calcium oxide, magnesia etc., two or more can also be used together.The esterification
Can at ambient pressure, under decompression, progress under any one environment or combination environment that pressurization is lower and nitrogen purging is lower.
(A) physical characteristic of composition is not particularly restricted, however, it is contemplated that the intermiscibility of (A) composition and matrix resin with
And the thermal-stable of contact adhesive/adhesive involved in the present invention, melt viscosity adaptability and heat-resisting confining force it is flat
If weighing apparatus etc., the weight average molecular weight of (A) composition is usually 800-4000 or so, and softening point is usually 70-180 DEG C or so, and
Acid number is 1-100mgKOH/g or so.
In (A) composition, crosslinking agent, antilubricant, preservative, antirust agent, pH adjusting agent, defoamer (silicon systems can be contained
Defoamer etc.), thickener, filler, antioxidant, water resistant additive, coalescents, pigment, the additive such as dyestuff.
(A) composition can also turn into the presence of emulsifying agent described later is made emulsion, is used as the resin for assigning adherence
Use.
Contact adhesive/adhesive of the present invention is the resin and the group of matrix resin of the imparting adherence containing the present invention
Compound.For example, said composition can be bonded as hot melt adhesive, solvent-borne type contact adhesive/adhesive and emulsion based pressure sensitive
Agent/adhesive is used, and is particularly suitable as hot melt adhesive and is used.
As matrix resin, various known matrix resins can be used, are not particularly restricted.Specifically, can be with
Enumerate for example：Vinyl copolymer, synthetic rubber based elastomers, acrylic acid series copolymer, acrylic acid series polymeric compounds emulsion, rubber
It is latex etc., according to the foregoing Utilization plan of contact adhesive/adhesive of the present invention, selects appropriate matrix resin.
For hot melt adhesive purposes, optimal ethylene based copolymer and/or synthetic rubber based elastomers.
As vinyl copolymer, it can enumerate for example：Ethylene-vinyl acetate copolymer, ethene-(methyl) alkyl acrylate
Base ester copolymer.As (methyl) alkyl acrylate, it can enumerate for example：(methyl) methyl acrylate, (methyl) propylene
Acetoacetic ester, (methyl) butyl acrylate, (methyl) 2-EHA etc., two or more can also be used together.
As synthetic rubber based elastomers, it can enumerate for example：SIS
(SIS), SBS (SBS), styrene-hydrogenated butadiene-styrene block copolymer
(SEBS) and styrene-ethylene/propylene-styrene copolymer (SEPS) etc., two or more it can also be used together.
It is used as acrylic acid series copolymer (in addition to foregoing ethene-(methyl) alkyl acrylate copolymer), Ke Yilie
Citing is such as：(methyl) glycidyl acrylate and (methyl) acrylic acid 2- hydroxyl ethyl esters；Containing (methyl) acrylic acid, fumaric acid,
The copolymer of maleic acid (acid anhydride), (methyl) acrylate of itaconic acid isoreactivity hydrogen-based and foregoing (methyl) alkyl acrylate
Deng two or more can also being used together.
As acrylic acid series copolymer emulsion, it can enumerate, by foregoing acrylic acid series copolymer in the presence of emulsifying agent
Emulsify the acrylic acid series copolymer emulsion formed.As the emulsifying agent, for example non-reacted emulsifying agent and/or reaction can be used
Property emulsifying agent.
As non-reacted emulsifying agent, it can enumerate for example：Dialkyl sulphosuccinate salt, alkane sulfonate, α-alkene
Sulfonated hydrocarbon, polyoxyethylene alkyl ether sulfosuccinate salt, polyoxyethylene styryl phenyl ether sulfosuccinate salt, naphthalene
The anionic properties such as sulfonic formaldehyde condensation compound, polyoxyethylene alkyl ether sulfuric acid, polyoxyethylene alkyl phenyl ether sulfuric acid breast
Agent；And polyoxyethylene alkyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitan fatty acid ester etc. are non-
Ionic emulsifier.
As reactive emulsifier, it can enumerate for example：Dredged with the hydrophilic groups such as sulfonic group, carboxyl and alkyl, phenyl etc.
Water base surfactant, and be the surfactant that there is carbon-to-carbon double bond in intramolecular., can be with as the carbon-to-carbon double bond
Enumerate for example：(methyl) pi-allyl, 1- acrylic, 2- methyl-1-propylenes base, vinyl, isopropenyl, (methyl) acryloyl group
Deng functional group.As the instantiation of reactive emulsifier, it can enumerate for example：At least there are an aforementioned functional groups in molecule
Polyoxyethylene alkyl ether, at least there is in molecule the polyoxyethylene phenyl ether and their sulfo group fourth of aforementioned functional groups
Two acid esters salt and sulfuric acid.It can also enumerate：At least there is the polyoxyethylene alkylphenyl of an aforementioned functional groups in molecule
Ether and its sulfosuccinate salt, its sulfuric acid, its phosphate ester salt, its aliphatic carboxylate or aromatic carboxylic acid salt.Moreover,
Acid phosphatase (methyl) acrylic ester emulsifying agent, the anhydride modified product of rosin shrinked glyceride acrylate can also be used
(referring to Japanese Unexamined Patent Publication 4-256429 publications), Japanese Unexamined Patent Application 63-23725 publications, Japanese Unexamined Patent Application 63-240931
Emulsifying agent described in publication, Japanese Unexamined Patent Application 62-104802 publications.
As rubber series latex, it can enumerate for example：Natural rubber latex, SB latex, neoprene
Latex etc., two or more can also be used together.
As the matrix resin beyond above-mentioned matrix resin, it can enumerate for example：Polyurethane resin, liquid polybutadiene,
Liquid polyisobutene, Pioloform, polyvinyl acetal, gelatin, mannosan, starch etc., two or more can also be used together.
The resin of the imparting adherence of the present invention and the usage amount of aforementioned substrates resin be not particularly restricted, however, logical
Often, the resin (solid constituent conversion) of adherence is assigned relative to 100 parts by weight, aforementioned substrates resin is 2-40 parts by weight or so
(solid constituent conversion).
, can resins containing other imparting adherences, various known in contact adhesive/adhesive of the present invention
Organic solvent, wax, crosslinking agent and aforementioned additive.
As the resin of other imparting adherences, it can enumerate for example：The raw pines such as gum rosin, wood rosin and Starex
Fragrant (in addition to belonging to the rosin of (a1) composition)；Their refined products, hydrogenation products, polymer and reinforcing product etc. are modified
Rosin；And the reaction product of the modified rosin and foregoing (a2) composition and/or (a3) composition etc..In addition to this it is possible to arrange
Lift：The Petropols such as C9 through-stones oleoresin, C5 through-stones oleoresin, C5/C9 through-stones oleoresin and their hydrogenation products；Note alkene
Resin and its hydrogenation products etc..
As organic solvent, it can enumerate for example：Acetone, MEK, toluene, benzene, ethyl acetate, chloroform and dimethyl methyl
Acid amides etc., two or more can also be used together.
As wax, it can enumerate for example：Beeswax, spermaceti and shellac wax etc. come from the wax of animal；Brazil wax, wood
Wax, rice bran wax and candelila wax etc. come from the wax of plant；Paraffin and microwax etc. come from the wax of oil；And lignite wax and
Ceresine etc. comes from the wax of mineral；Two or more it can also be used together.
As crosslinking agent, by adding such as polyisocyanate compound, polyamine compounds, melmac, urea
The crosslinking agents such as resin, epoxy resin, can also further improve cohesive force, heat resistance.It is especially excellent in these crosslinking agents
Choosing uses polyisocyanate compound, as its instantiation, can enumerate following various known polyisocyanate compounds：
1,6- hexamethylene diisocyanates, tetramethylene diisocyanate, IPDI, the sub- isocyanic acid of dimethylbenzene two
Ester, toluene di-isocyanate(TDI), 4,4 '-'-diphenylmethane diisocyanate etc..Moreover, as needed, acrylic acid series pressure of the invention
Sensitive adhesive/adhesive compound can take the circumstances into consideration using filler, antioxidant, ultra-violet absorber etc..Moreover, not departing from
In the range of the purpose of the present invention, acrylic pressure-sensitive adhesive/adhesive compound of the invention can also with it is various known
The resin of imparting adherence be used together.
Embodiment
The present invention is described in detail below by way of embodiments and comparative examples, however, the scope of the present invention is not by these
Example is limited.
In embodiments, the dihydro agate in raw material rosin is determined using following gas chromatography-mass spectrometry analysis device
Sour (DHAA), rosin acid (AA) and dehydroabietic acid (DAA) content.In the assay, sample (rosin) 0.005g is dissolved
In (0.2 mole, of methanol solution, the Japan ジ ー エ Le サ of phenyl trimethicone ammonium hydroxide (PTHA) of methylating reagent on 0.5g posts
イ エ Application ス (strain)), 1 μ l are injected into gas chromatography-mass spectrometry analysis (GC/MS) and are measured.From the methyl ester products of resin acid
Each content is determined.Use device is gas chromatography-mass spectrometry analysis device (manufacture name " Agilent 6890 ", " Agilent
5973N”；Agilent technologies are manufactured) and commercially available post (manufacture name " Advance-DS ", Japan's letter and chemical industry
(strain) is manufactured).
In embodiments, the weight average molecular weight (Mw of rosin ester：Polystyrene scaled value) obtain under the following conditions.
Analytical equipment：HLC-8220 (this East ソ ー (strain) are manufactured)
Post：TSKgelSuperHM-L × 3 piece
Eluent：Tetrahydrofuran
Inject sample concentration：5mg/mL
Flow：0.6mL/min
Injection rate：100μL
Column temperature：40℃
Detector：RI
In embodiments, the softening point (Sp (DEG C)) of rosin ester is determined according to JIS K 2531 ring and ball method.
1. assign the synthesis of the resin of adherence
Production Example 1
100 parts of Indonesia are produced into gum rosin and are dissolved in 100 parts of dimethylbenzene, it is water-soluble using 5 parts of 48%NaOH in room temperature
Liquid, 33 parts of water are extracted 1 time.Then water layer (extract solution) is neutralized using watery hydrochloric acid, the resin acid that of dissociating uses 33 part two
After toluene is extracted, dimethylbenzene is distilled off at 200 DEG C, the resin acid composition of the dihydro agathic acid containing 90 weight % is obtained
(acid number 290mgKOH/g).
Embodiment 1
In the reaction vessel equipped with agitating device, cooling tube, thermometer and nitrogen ingress pipe, 50 parts of India Ni Xi are added
Gum rosin (10 weight % dihydro agathic acids, 35 weight % rosin acids, the 5 weight % dehydroabietic acids, acid number of Asia production
190mgKOH/g, 80 DEG C of softening point；Hereinafter referred to as ID rosin) and 50 parts in domestic gum rosin (0 weight % dihydro agathic acids,
50 weight % rosin acids, 5 weight % dehydroabietic acids, acid number 170mgKOH/g, 75 DEG C of softening point；Hereinafter referred to as CN rosin),
200 DEG C are allowed to melt.1 part of fumaric acid is added then to reaction system, is reacted 1 hour at 200 DEG C.Then, to the molten of the temperature
Melt 15 parts of pentaerythrites of addition in thing, under nitrogen flowing, esterification is carried out 10 hours at 280 DEG C.Thereafter, subtracted by 3 hours
Pressure processing, has synthesized fortified rosin ester.Physical characteristic is shown in table 1.
Embodiment 2
Into reaction vessel similarly to Example 1,100 parts of ID rosin are added, are allowed to melt at 200 DEG C.Then, to this
15 parts of pentaerythrites are added in the fused mass of temperature, under nitrogen flowing, esterification is carried out 10 hours at 280 DEG C, then, passes through
3 hours reduced pressure treatments, have synthesized rosin ester.Physical characteristic is shown in table 1.
Embodiment 3
Into reaction vessel similarly to Example 1,30 parts of 70 parts of CN rosin and ID rosin are added, is allowed to molten at 200 DEG C
Melt.Then, 15 parts of pentaerythrites are added into the fused mass of the temperature, under nitrogen flowing, esterification 10 are carried out at 280 DEG C small
When, then, by 3 hours reduced pressure treatments, synthesize rosin ester.Physical characteristic is shown in table 1.
Embodiment 4
Into reaction vessel similarly to Example 1, the resin acid group that 98 parts of ID rosin and 2 parts of Production Examples 1 are obtained is added
Compound, is allowed to melt at 200 DEG C.Then, 14 parts of pentaerythrites are added into the fused mass of the temperature, under nitrogen flowing, 280
DEG C esterification 12 hours is carried out, then, by 5 hours reduced pressure treatments, synthesized rosin ester.Physical characteristic is shown in table 1.
Comparative example 1
Into reaction vessel similarly to Example 1,100 parts of CN rosin are added, are allowed to molten in 200 DEG C under nitrogen flowing
Melt.Then, 1 part of fumaric acid is added to the reaction system, is reacted 1 hour at 200 DEG C.Then, add into the fused mass of the temperature
Enter 15 parts of pentaerythrites, under nitrogen flowing, esterification is carried out 10 hours at 280 DEG C.Thereafter, by 3 hours reduced pressure treatments, close
Into fortified rosin ester.Physical characteristic is shown in table 1.
Comparative example 2
Into reaction vessel similarly to Example 1,100 parts of CN rosin are melted, 5 parts of fumaric acid are added, it is anti-at 200 DEG C
Answer 1 hour.Then, 13 parts of pentaerythrites are added, 280 DEG C are warming up under nitrogen flowing, it is small to carry out esterification 10 in the temperature
When.Thereafter, by 3 hours reduced pressure treatments, fortified rosin ester has been synthesized.Physical characteristic is shown in table 1.
Comparative example 3
Into reaction vessel similarly to Example 1,100 parts of CN rosin are melted, are allowed to melt at 200 DEG C.Then, to
15 parts of pentaerythrites are added in the fused mass of the temperature, under nitrogen flowing, esterification is carried out 10 hours at 280 DEG C, then, led to
3 hours reduced pressure treatments are crossed, rosin ester has been synthesized.Physical characteristic is shown in table 1.
Table 1
In table 1, DHAA represents dihydro agathic acid, and AA represents rosin acid, and DAA represents dehydroabietic acid.
2. the preparation of hot melt adhesive
By (A1) composition of embodiment 1 and commercially available ethylene-vinyl acetate copolymer (trade name EVA#220, Japan three
Well デ ュ Port Application Port リ ケ ミ カ Le (strain) manufacture) and microwax (trade name Hi-Mic-1080, Japan essence wax (strain) manufacture) press
Mixed according to weight than 4/4/2, by being allowed to melt under heating, be prepared for hot melt adhesive.
Thermal-stable is tested
The foregoing hot melt adhesives of 25g are weighed, respectively at the 24th hour, the 48th hour and the 72nd hour, according to following standard
Visually confirmed it whether there is muddy and peeling at the end of being heated in 180 DEG C of drying machine with the wind.As a result it is shown in table 2.
○：Muddiness, without peeling
△：Muddiness, somewhat produces peeling
×：Muddiness, produces peeling strongly
The measure of melt viscosity
Use commercially available Brookfield viscometer (rotor：HM-3, rotating speed：Foregoing hot melt adhesive 3rpm) is determined respectively at 150 DEG C
With 180 DEG C of viscosity.As a result it is shown in table 2.
Intermiscibility
(A1) composition 2g and EVA#220 2g of embodiment 1 are put into test tube, mixed under heating, are made after its melting, will
The fused mass is further heated to 200 DEG C, then places cooling, determines the temperature (cloud point) for producing muddiness in appearance.For
The rosin ester of other embodiments and comparative example, is similarly operated, and prepares mixture, equally determines its cloud point.As a result it is shown in table
2。
Heat-resisting confining force
By the hot melt adhesive coating involved by embodiment 1 on aluminum substrates, cut off according to long 7.5cm, width 2.5cm.Make
Be crimped on other aluminium adherend after, 23 DEG C place 1 day.Then, using commercially available creep test device (product
Name：It is equipped with holding force tester (constant temperature and humidity cabinet pays confining force Try test Machine), the Japan's テ ス タ ー industries of constant temperature and humidity cabinet
(strain) is manufactured), under conditions of loading 1kg, temperature 60 C, measure reaches the time that the loading article is fallen, according to following marks
Standard evaluates heat-resisting confining force.
○：More than 2 hours
△：1.5 hours less than 2 hours
×：Less than 1.5 hours
Table 2
Claims (6)
1. the resin of the imparting adherence containing rosin ester (A), wherein, foregoing rosin ester (A) is to be represented containing following formulas
Binary diterpene carboxylic acid rosin (a1) and polyalcohol (a2) be reacted constituent obtained from.
[changing 1]
2. the resin of adherence is assigned as claimed in claim 1, wherein, foregoing (a1) composition contains rosin acid and dehydrogenated rosin
Acid.
3. the resin of adherence is assigned as claimed in claim 1 or 2, wherein, previous reaction composition contains α, β-unsaturation carboxylic
Acids (a3).
4. the contact adhesive of resin and matrix resin containing the imparting adherence described in any one in claim 1-3/
Adhesive.
5. resin and the hot melt adhesive of matrix resin containing the imparting adherence described in any one in claim 1-3.
6. hot melt adhesive as claimed in claim 5, wherein, aforementioned substrates resin contains ethylene-vinyl acetate copolymer.
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| JP2015255861 | 2015-12-28 | ||
| JP2015-255861 | 2015-12-28 | ||
| JP2016-190628 | 2016-09-29 | ||
| JP2016190628A JP6996077B2 (en) | 2015-12-28 | 2016-09-29 | Adhesive-imparting resin, adhesive / adhesive, hot melt adhesive |
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| CN106995668A true CN106995668A (en) | 2017-08-01 |
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| CN201611160305.4A Pending CN106995668A (en) | 2015-12-28 | 2016-12-15 | Assign resin, contact adhesive/adhesive, the hot melt adhesive of adherence |
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| JP (1) | JP6996077B2 (en) |
| CN (1) | CN106995668A (en) |
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| JP2018083868A (en) * | 2016-11-21 | 2018-05-31 | 旭化学合成株式会社 | Hot-melt adhesive composition and bonding method using the same |
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| JP6996077B2 (en) | 2022-01-17 |
| TW201736431A (en) | 2017-10-16 |
| JP2017119824A (en) | 2017-07-06 |
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